JP3279437B2 - Antifouling paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint composition using a metal-containing resin that hydrolyzes in seawater as a binder.

[0001]

BACKGROUND OF THE INVENTION Bottom skin of a vessel below sea level;
Various types of marine organisms adhere to the surface of marine structures and fishing nets, which hinders efficient operation of ships.
In marine structures and fishing nets, problems such as a significantly shortened service life occur, and as a countermeasure, underwater antifouling paint compositions containing various antifouling agents are used. As a typical antifouling paint conventionally used, an antifouling agent is blended with a vehicle component comprising a resin such as a vinyl resin, an alkyd resin, and a chlorinated rubber which are insoluble in seawater and a rosin which is soluble in seawater. Dissolved matrix type antifouling paints, such as dissolved matrix type antifouling paints and copolymers containing triorganotin-containing monomers that gradually hydrolyze in sea water as a vehicle component and an antifouling agent blended as necessary There is. However, the antifouling agent is eluted together with rosin into seawater, and the insoluble matrix-type antifouling paint exhibiting an antifouling effect cannot be expected to have a long-term stable antifouling effect, and rosin and the antifouling agent eluted. Later, since the resin component insoluble in seawater remains as a coating film and forms a skeleton structure, particularly when applied to a ship, the frictional resistance between the seawater and the coating surface increases, the speed decreases, and there is a disadvantage that fuel efficiency increases. . On the other hand, the dissolving matrix type antifouling paint has an antifouling effect, but has problems in health and safety and environmental conservation.

Recently, an antifouling paint containing a hydrolyzable polyester resin and a water-insoluble resin as a vehicle component without using an organotin-containing resin has been developed as an intermediate type between the above two paints (Japanese Patent Publication No. Hei 3 (1994)). -46501, JP-A-4-23020). This antifouling paint uses a single condensate of an oxyacid such as lactic acid and a water-insoluble resin as a vehicle component and does not contain organotin.
Although it is a paint excellent in environmental preservation, it has the drawback that the resin component insoluble in seawater remains as a coating film and forms a skeleton structure as in the case of the insoluble matrix type antifouling paint because a water-insoluble resin is used in combination. was there. Therefore, antifouling paints using only a condensate of oxyacid as a vehicle component have been considered, but when the molecular weight of the condensate is increased to a level of tens of thousands or more, it is dissolved only in a special organic solvent such as chloroform. It does not dissolve in ordinary organic solvents for coatings, and has drawbacks in coating and coating workability. On the other hand, when the molecular weight is reduced to 10,000 or less, it dissolves in ordinary organic solvents for coating, but it is dissolved in seawater. Has a drawback that a long-term antifouling effect cannot be obtained because the hydrolysis rate is too high and the hydrolysis rate cannot be adjusted.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of conventional antifouling paints as described above, and is useful for applications such as the bottom skin of ships below sea level, marine structures, and fishing nets. It is an object of the present invention to provide a coating composition which can effectively prevent various marine organisms from adhering to the surface for a long period of time and is excellent in safety and health and environmental protection.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted research to overcome such a situation, and as a result, have found that other specific metal-containing resin can be used as a binder without containing organotin. As a result, the present inventors have found that a coating composition having a long-term antifouling property and excellent in safety and health and environmental protection can be obtained, thereby completing the present invention. That is, the present invention
Provided is an antifouling paint composition using, as a binder, a resin having a group represented by the following formula (I) at the side chain terminal. —CO—O—M—O—Si (R) ₃ (wherein M represents a zinc or copper atom; R is the same or different and represents a hydrogen atom, a halogen atom, a hydroxyl group, an organic group , An organo (poly) siloxane group,
A silyl group, a mercapto group, or a substituted product thereof is shown. In addition, as the material group, an alkyl group, an aryl group,
An alkenyl group, an alkoxyl group, a phenoxyl group, an acyl group or a substituted product thereof is mentioned as a typical example. Hereinafter, the present invention will be described in detail.

[0005] The binder constituting the coating composition of the present invention comprises:
It is synthesized by various methods.
It is synthesized by introducing a group represented by the above formula (I) into a resin having a carboxyl group-containing ordinary coating resin such as 50, preferably 60 to 300 acrylic resin or polyester resin as a base resin. Suitable binders are preferred. When the acid value of the base resin is smaller than the above range, the amount of the group represented by the formula (I) is reduced, and the long-term antifouling property tends to decrease. The physical properties of the film tend to decrease, and cracks and the like tend to occur.

The acrylic resin serving as the base resin is appropriately combined with various polymerizable unsaturated monomers so that the acid value of the obtained acrylic resin falls within the above range.
It is manufactured by reacting at ~ 180 ° C for 2 to 10 hours. Examples of the polymerizable unsaturated monomer used here include (meth)
Polymerizable unsaturated carboxylic acids such as acrylic acid, crotonic acid, maleic acid, itaconic acid, phthalic acid, and citraconic acid or acid anhydrides thereof; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -(Meth) acrylates such as ethylhexyl (meth) acrylate and lauryl (meth) acrylate; aromatic vinyl monomers such as styrene and vinyltoluene; hydroxyl groups such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate Glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; perfluorocyclohexyl (meth) acrylate, propyl perfluorooctanesulfonamidoethyl (meth) acyl Rate, vinyl fluoride, fluorine-containing vinyl monomers such as vinylidene fluoride diethyl (meth) acrylamide, (meth) nitrogen-containing vinyl monomers such as acrylamide, vinyl ethyl ether, vinyl ether monomers such as vinyl ether; vinyl acetate,
Vinyl esters such as vinyl benzoate; other (meth) acrylic acid chlorides, vinyl chloride, vinylidene chloride,
(Meth) acrylonitrile and the like.

The polyester resin used here is a polybasic acid or a polyhydric alcohol with an acid anhydride thereof, and if necessary, a monobasic as a molecular weight regulator such as benzoic acid or various animal and vegetable oil fatty acids. While dehydrating in the presence or absence of a catalyst using an acid in combination,
It is produced by heating and reacting at a temperature of 30 ° C. Examples of polybasic acids or acid anhydrides used in the production of this polyester resin include oxalic acid, succinic acid, succinic anhydride,
Linear polybasic acids such as adipic acid, azelaic acid and sebacic acid or acid anhydrides thereof; phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride,
Aromatic base acids such as hexahydrophthalic acid, hexahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, and cyclohexanedicarboxylic acid or anhydrides thereof; maleic acid There are unsaturated polybasic acids such as maleic anhydride, fumaric acid, and itaconic acid or acid anhydrides thereof. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butanediol,
There are 1,6-hexanediol, diethylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and cyclohexanedimethanol. Other examples of the base resin include an epoxy resin, an acryl-modified epoxy resin, an acryl-modified polyester resin, an alkyd resin, and a fluororesin. In particular, in the present invention, an acrylic resin having excellent adhesion when applied over the old antifouling coating film formed by the coating material of the present invention is preferable.

In order to introduce the group represented by the above formula (I) into these base resins, the following compounds are used. (i) zinc or copper oxides, chlorides, hydroxides, sulfides, or acetic acid, lactic acid, butyric acid, propionic acid,
Zinc salt or copper salt of an organic basic acid which is a reaction product with an organic basic acid such as (meth) acrylic acid, oxalic acid, valeric acid, enanthic acid, cyclohexanecarboxylic acid, propiolic acid, glycolic acid, etc. (Ii) silane compounds such as ethyl orthosilicate, silanol, silanediol, silanetriol, disilanehexol, methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane; Siloxane compound: (R) ₃ Si-O- (Si (R) ₂ -O-) _n -Si (R) ₃ or (R) ₃ Si-O- (
Si (R) ₂ -O-) _m- (Si (R) ₂ -0-) _n -Si (R) ₃ (wherein R is the same or different group, and at least one is a hydroxyl group or an alkoxy group And the remainder is a hydrogen atom, a halogen atom, a mercapto group, or a material group such as an alkyl group, an aryl group, an alkenyl group, an alkoxyl group, a phenoxyl group, an acyl group, or a substituted product thereof; , 0 or an integer of 1 or more.);

[0009] DC6-2230, DC3037, DC3
074, SH6018, SR2402, QP8-531
A silicone intermediate having a hydroxyl group or an alkoxy group which is known as a commercially available product such as No. 4 (both trade names manufactured by Dow Corning Toray Silicone Co., Ltd.); and having at least one hydroxyl group or an alkoxy group in a silicon atom. Compounds (hereinafter collectively referred to as “silicon compounds”). Preferably, the binder of the present invention is obtained by subjecting the metal compound (i) and the silicon compound (ii) to a heat reaction in a solvent at a temperature of about 70 to 200 ° C. in the presence or absence of a catalyst. The reaction product and the base resin having a carboxyl group are reacted by heating at a temperature of about 110 ° C to 200 ° C. Alternatively, the binder of the present invention can be produced by reacting the metal compound (i) with the base resin having a carboxyl group and then reacting the silicon compound (ii). is there.

The production method described above is a method of introducing a group represented by the formula (I) into a base resin. Other methods include the above-mentioned polymerizable unsaturated carboxylic acid or its acid anhydride and the above-mentioned metal. A method of reacting the compound (i) with a polymerizable unsaturated monomer and then copolymerizing the compound with another polymerizable unsaturated monomer, and further reacting the silicon compound (ii) to produce a binder, or the metal compound (i) and a silicon compound. Reacting the compound (ii), then reacting the reaction product with the polymerizable unsaturated carboxylic acid or its acid anhydride, and further copolymerizing with another polymerizable unsaturated monomer to produce a binder. Or the like.

The binder thus obtained has a water-repellent property while the group represented by the formula (I) is gradually hydrolyzed in sea water and the group remains without being hydrolyzed. Since it has an effect, it has a long-term stable antifouling effect due to a synergistic effect of both. In order to exhibit such an antifouling effect, the content of the zinc or copper atom in the group represented by the formula (I) is preferably 1 to 20% by weight, particularly preferably 1. A suitable range is 5 to 15% by weight. In addition, if the amount of zinc or copper atoms is less than the above range, the antifouling effect is reduced, and conversely, if the amount is large, the amount of hydrolysis is too large and the coating film is likely to disappear in an early period, and the long-term antifouling property is reduced. It tends to decrease.

The weight-average molecular weight of the resin as the binder varies depending on the type of the resin, but is usually from 2,000 to 150,000.
00, preferably 5,000 to 50,000.
When the weight average molecular weight is less than the above range, the drying properties and various physical properties of the obtained coating film tend to decrease, while when the weight average molecular weight exceeds the above range, the storage stability of the paint tends to decrease. The resin as a binder thus obtained is a solvent such as an aromatic solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or an ester solvent such as ethyl acetate, butyl acetate or cellosolve acetate. It is diluted to a desired resin concentration by using an alcohol-based solvent such as butyl alcohol or the like, or an ether-based solvent such as dioxane or tetrahydrofuran, and used as a vehicle component of an antifouling paint. The antifouling coating composition of the present invention comprises the above resin solution as a vehicle component, and further, if necessary, a known antifouling agent, a copper compound of a monovalent organic acid having 5 to 18 carbon atoms, a solvent, a coloring pigment, and a constitution. Pigment, rosin,
It is composed of a mixture of various additives such as a plasticizer and an antifoaming agent, an anti-settling agent and a leveling agent.

The antifouling agent used as required in the present invention need not be particularly limited.
Cuprous oxide, basic copper carbonate, copper thiocyanate, copper hydroxide, cuprous rhodan, manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino- s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethylchlorophenylurea, zinc ethylenebisdithiocarbamate, 4,5-
Dichloro-2-N-octyl-3 (2H) inchazolone, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N'-phenyl (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 2, There are 4,6-trichlorophenylmaleimide, 2-pyridinethiol-1-oxide zinc salt and the like, and these can be used alone or in combination.

The copper compound of a monovalent organic acid having 5 to 18 carbon atoms which is optionally used in the present invention is typically a hydroxide or an oxide of a monovalent organic acid having 5 to 18 carbon atoms and copper. Or a direct method of dehydration and filtration, or a monovalent organic acid having 5 to 18 carbon atoms is converted to a water-soluble salt such as a sodium salt, and a water-soluble salt of copper, such as a sulfate or a nitrate. Alternatively, it is produced by a double decomposition method or the like in which a carbonate or the like is added, an ion exchange reaction called metathesis is performed, and washing, dehydration, and filtration are further performed. The monovalent organic acids having 5 to 18 carbon atoms include valeric acid, caproic acid, caprylic acid, undecylic acid, lauric acid, myristic acid, stearic acid, undecylenic acid, linoleic acid, versatic acid (manufactured by Shell Chemical Company). ), Eacid-9, -10 (made by Idemitsu Oil Co., Ltd.), neodecanoic acid (made by Exxon Chemical Co., Ltd.)
And various fatty acids and synthetic fatty acids.

The solvent used as required in the present invention is the same as the solvent for the resin described above. The coloring pigment, extender, rosin, plasticizer, various additives, and the like used as necessary in the present invention are the same as those used in ordinary antifouling paints. When preparing the antifouling coating composition of the present invention, the resin is 15 to 60% by weight, preferably 20 to 40% by weight, the antifouling agent is 0 to 45% by weight, preferably 10 to 40% by weight, and the monovalent organic acid is used. It is suitable to add 0 to 20% by weight, preferably 1 to 10% by weight of a copper compound, and 20 to 70% by weight, preferably 30 to 50% by weight of a solvent (solvent). When the amount of the resin is less than the above range, the strength of the coating film or the like tends to decrease, while when the amount is too large, the coating workability or the like tends to deteriorate. The antifouling paint composition of the present invention is prepared by mixing and dispersing the resin and other components by a single or divided mixing and dispersing with a usual paint producing apparatus such as a ball mill and a disper. The antifouling paint composition of the present invention thus prepared is dried on a ship or marine structure by airless spray coating, air spray coating, roller coating, brush coating or the like as it is or after adjusting the viscosity with a solvent. It is preferably applied later to a thickness of about 30 to 300 μm, preferably 80 to 200 μm.

[0016]

According to the present invention, it has a long-term antifouling property substantially equal to that of a dissolution-matrix-type antifouling paint containing an organotin-containing resin as a vehicle component, and can control the hydrolysis rate of a coating film. The coating film formed by the coating material of the present invention has excellent adhesion when newly applying a coating material, that is, excellent recoating property, and furthermore, since it does not contain an organotin-containing resin, there is a problem in health and safety and environmental protection. As a result, an epoch-making antifouling paint having a small number was obtained.

[0017]

The present invention will be described below in more detail with reference to examples. In the examples, “parts” and “%” are based on weight. <Preparation of base resin varnish A> In a separable flask equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introduction pipe,
After adding 80 parts of xylene and 20 parts of n-butanol and raising the reaction temperature to the reflux temperature (100 to 110 ° C.), under a nitrogen gas atmosphere, 48.2 parts of ethyl acrylate, 19.7 parts of 2-ethylhexyl acrylate, A mixed solution consisting of 32.1 parts of acrylic acid and 1.5 parts of azobisisobutyronitrile was added dropwise over 3 hours.
0.2 parts of azobisisobutyronitrile and 7 parts of xylene were added three times every minute, and the mixture was further reacted for 2 hours. The obtained base resin varnish A had a solid content of 45.1% and an acid value (solid content).
250, weight average molecular weight 10,200. <Preparation of base resin varnish B> In the method of preparing base resin varnish A, the mixed solution was mixed with n-butyl acrylate 70.0.
Part, n-butyl methacrylate 7.0 parts, methacrylic acid 2
The reaction was carried out in the same manner except that the mixture was changed to a mixed solution consisting of 3.0 parts and 1.0 part of azobisisobutyronitrile. The solid content was 45.0%, the acid value (solid content) was 150 weight average molecular weight 21, 3
00 base resin varnish B was prepared.

<Preparation of base resin varnish C> In the preparation method of base resin varnish A, 14.7 parts of methyl methacrylate, 75.0 parts of ethyl acrylate, 10.3 parts of acrylic acid and azobisisobuty The reaction was carried out in the same manner except that the mixture was changed to 0.7 parts of lonitrile, and the reaction temperature was changed to 90 ° C. The solid content was 44.9%, the acid value (solid content) was 80, and the weight average molecular weight was 35,500. Was prepared. <Preparation of Metal-Containing Intermediate Varnish D> In a separable flask equipped with a stirrer, a thermometer, a condenser with a water separator, and a nitrogen inlet tube, 15.0 parts of xylene, a silicone intermediate [“S
H6018 "(trade name, manufactured by Dow Corning Toray Silicone Co., Ltd.); average molecular weight 1,600, hydroxyl group content 6.4%]
217.2 parts and 53.1 parts of 2-ethylhexyl alcohol were added, and the reaction temperature was raised from 120 ° C to 14 ° C under a nitrogen gas atmosphere.
At 0 ° C., 6.6 parts of condensed water were removed and cooled. Next, 29.7 parts of zinc acetate and 300 parts of xylene were added, and the reaction temperature was 12
Perform deacetic acid reaction while increasing from 0 ° C to 140 ° C,
The amount of deacetic acid was quantified, and the reaction was terminated at a reaction rate of 50% as zinc acetate and cooled. The solid content of the obtained metal-containing intermediate varnish D was 48.3%.

<Preparation of Metal-Containing Intermediate Varnish E> In the above separaple flask, 400.0 parts of xylene, 158.0 parts of dimethyldiethoxysilane, and 10 parts of copper hydroxide
3.6 parts and 2-ethylhexyl alcohol 138.4
Part under nitrogen gas atmosphere at a reaction temperature of 80 ° C to 1
The reaction was carried out at 30 ° C. while removing ethanol, the amount of ethanol removed was quantified, and the reaction was terminated at a reaction rate of 90% as dimethyldiethoxysilane, followed by cooling. The solid content of the obtained metal-containing intermediate varnish E was 46.5%. <Preparation of Metal-Containing Intermediate Varnish F> In the separable flask, 15.0 parts of xylene, 219.3 parts of a silicone intermediate [“SH6018” (trade name, manufactured by Dow Corning Toray Silicone Co., Ltd.)] and 2-ethylhexyl 53.4 parts of alcohol was added and 6.6 of condensed water was added under a nitrogen gas atmosphere at a reaction temperature of 120 ° C to 140 ° C.
The part was removed and cooled. Next, 27.3 parts of copper acetate and 300 parts of xylene were added, a deacetic acid reaction was carried out while increasing the reaction temperature from 120 ° C. to 140 ° C., and the amount of deacetic acid was quantified.
When the reaction rate as copper acetate was 50%, the reaction was terminated.
Cool. The solid content of the obtained metal-containing intermediate varnish F was 49.0%.

<Preparation of Metal-Containing Resin Varnish M-1> A base resin varnish A10 was placed in a separable flask equipped with a stirrer, a thermometer, a condenser tube with a water separator, and a nitrogen inlet tube.
0 parts, 857 parts of the metal-containing intermediate D and 288 parts of xylene were added, and the reaction temperature was increased to reflux temperature (11
The temperature was raised to 8 to 140 ° C.), and a deacetic acid reaction was performed. When the amount of deacetic acid reached 10.8 parts (conversion rate: 90%), the reaction was completed. During the reaction, acetic acid was dissolved in the solvent, so that the reaction was carried out while removing the solvent from time to time and replenishing xylene with the removed amount. The obtained metal-containing resin varnish M-1 had a solid content of 37.8%, a weight average molecular weight of the resin of 15,300, a Zn content of the resin of 3%, and a Si content of 17.3 %.
Met.

<Preparation of Metal-Containing Resin Varnish M-2> 100 parts of a base resin varnish A was placed in the separable flask.
122.6 parts of a metal-containing intermediate varnish E and 53 parts of xylene were added, and the reaction temperature was increased to a reflux temperature (11
8 to 140 ° C.), and a dehydration reaction is performed.
The time when 2 parts (reaction rate 89%) was reached was regarded as the reaction end point. The obtained metal-containing resin varnish M-2 has a solid content of 38.4%,
Weight average molecular weight of resin 28,700, Cu content in resin 12.9
%, And the amount of Si was 5.7%. <Preparation of Metal-Containing Resin Varnish M-3> 100 parts of the base resin varnish C, 39 parts of the metal-containing intermediate E and 32 parts of xylene were placed in the separable flask, and the reaction temperature was adjusted to the reflux temperature (118 to 140) under a nitrogen gas atmosphere. ° C), and a dehydration reaction is carried out. The amount of dehydration is 1.0 part (reaction rate 87%)
At which point the reaction end point was reached. The obtained metal-containing resin varnish M-3 had a solid content of 38.2%, a weight average molecular weight of the resin of 39,800, a Cu content of the resin of 6.5%, and a Si content of 2.9%.

<Preparation of Metal-Containing Resin Varnish M-4> The base resin varnish B10 was placed in the separable flask.
0 parts, 505 parts of the metal-containing intermediate F and 185 parts of xylene were added, and the reaction temperature was increased to a reflux temperature (11
The temperature was raised to 8 to 140 ° C.), and the acetic acid reaction was carried out. When the amount of acetic acid was 6.5 parts (reaction rate: 90%), the reaction was completed. During the reaction, acetic acid was dissolved in the solvent, so that the reaction was carried out while removing the solvent from time to time and replenishing xylene with the removed amount. The obtained metal-containing resin varnish M-4 had a solid content of 38.5% and a weight average molecular weight of 2 for the resin.
5,100, Cu content 2.7% in resin, Si content 16.1
%Met.

Examples 1 to 4 and Comparative Examples 1 and 2 The components shown in Table 1 were kneaded and dispersed to produce antifouling paints of Examples 1 to 4 and Comparative Examples 1 and 2. Each of these antifouling paints
The steel sheet coated with the rust-preventive paint was applied by air spray coating to a dry film thickness of 150 μm and dried. When the obtained test plate was subjected to an antifouling test and a film thickness reduction test, the results shown in Tables 2 and 3 were obtained, respectively.
The test was performed based on the following method. <Antifouling test method> In Toba Bay, Toba City, Mie Prefecture, a test plate was submerged in the sea, and the appearance of the coating film was observed. Evaluation criterion 5: No deposit was observed on the test plate. 4: Adhesion of thin slime was observed on the test plate. 3: Thick slime adhered to the test plate. 2: Adherence of large animals and plants is slightly observed. 1: Large attachment of large animals and plants is observed. <Test method for measuring decrease in film thickness> A test plate was mounted on a rotor having a peripheral speed of 15 knots, rotated in the sea, and the degree of decrease in film thickness was measured every three months. The numerical values in Table 4 are the difference (unit: μm) between the initial film thickness measured by a micrometer and the film thickness measured every three months.

[0024]

[Table 1] Table 1 (Unit: parts by weight) Example Comparative example Composition 1 2 3 4 1 2 Metal-containing resin varnish M-1 59.5 〃 M-2 58.6 〃 M-3 58.9 〃 M-4 58.4 Rosin 15 Vinyl chloride resin varnish (solid content 50%) 20 Organotin methacrylate copolymer varnish Note 1) 45 Chlorinated paraffin 5 Cuprous oxide 35 35 35 35 35 35 35 Talc 5 5 5 5 5 5 Valve 3 3 3 3 3 3 Xylene 10 10 10 10 12 15 Methyl isobutyl ketone 2 2 2 2 ─────────────────────────────────── Note 1) Tributyltin methacrylate / methyl methacrylate (65/35) varnish with a solid content of 50%

[0025]

[Table 2] Table 2 (Results of antifouling test) Number of months of immersion 3 6 9 12 18 24 30 36 Example 1 5 5 5 5 5 5 5 5 2 5 5 5 5 5 5 5 5 3 5 5 5 5 5 5 5 5 4 5 5 5 5 5 5 5 5 Comparison Example 1 5 5 5 5 5 5 5 5 5 2 4 4 4 3 2 1 1 1 1 1

[0026]

[Table 3] Table 3 (Film thickness reduction measurement test results) Number of immersion months 3 6 9 12 Example 1 25 53 80 104 2 27 50 70 98 3 18 33 50 70 4 21 40 63 88 Comparative example 1 16 40 68 90 25 6 8 9

As is clear from the test results in Tables 2 and 3, the paints of Examples 1 to 4 of the present invention were prepared by dissolving the organotin-based dissolving matrix of Comparative Example 1 which is conventionally regarded as having a problem on safety and health. It had almost the same antifouling properties as a type antifouling paint.
Also, the amount of decrease in the film thickness was almost uniform, indicating that the solubility of the coating film could be controlled. On the other hand, Comparative Example 2, which is an insoluble matrix type antifouling paint, had poor long-term antifouling properties. Further, in Examples 1 to 4, the test plate 12 months after the thickness reduction measurement test was washed with water and dried, and the same paint was applied again on the old coating film in the same manner and dried. The plate was mounted on a rotor having a peripheral speed of 15 knots, rotated in the sea, and the state of the coating film after 6 months was observed. As a result, there was no peeling of the coating film and the recoating property was excellent.

Continued on the front page (72) Inventor Yoshiyuki Iwase 68-27, Nishitoyama, Nishinasuno-machi, Nasu-gun, Tochigi Prefecture References JP-A-2-196869 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 5/16

Claims (2)

(57) [Claims] 1. An antifouling coating composition comprising a binder having a resin having a group represented by the following formula at a terminal end of a side chain. —CO—O—M—O—Si (R) ₃ (wherein M represents a zinc or copper atom; R is the same or different and represents a hydrogen atom, a halogen atom, a hydroxyl group, an organic group , An organo (poly) siloxane group,
A silyl group, a mercapto group, or a substituted product thereof is shown. ) 2. The antifouling coating composition according to claim 1, wherein the resin is an acrylic resin or a polyester resin.